Substrate drying method and substrate processing apparatus

ABSTRACT

A substrate drying method includes a sublimation-agent-liquid-film placing step of placing a liquid film of a liquid sublimation agent on the front surface of the substrate, a high vapor-pressure liquid supply step of supplying a high vapor-pressure liquid that has vapor pressure higher than the sublimation agent and that does not include water to a rear surface that is a surface on a side opposite to the front surface in the substrate, a vaporizing/cooling step of, after the liquid film of the sublimation agent is placed on the front surface of the substrate, stopping supplying the high vapor-pressure liquid, and, as a result, losing vaporization heat in response to vaporization of the high vapor-pressure liquid, and, as a result, cooling the sublimation agent, and, as a result, solidifying the liquid film of the sublimation agent and a sublimating step of sublimating a sublimation-agent film.

BACKGROUND OF THE INVENTION 1. Field of the Invention

The present invention relates to a substrate drying method and a substrate processing apparatus. Examples of substrates to be processed include semiconductor wafers, substrates for liquid crystal displays, substrates for FPDs (Flat Panel Displays) such as organic EL (electroluminescence) displays, substrates for optical disks, substrates for magnetic disks, substrates for magneto-optical disks, substrates for photomasks, ceramic substrates, and substrates for solar cells.

2. Description of the Related Art

In a manufacturing process of a semiconductor device, a front surface of a substrate, such as a semiconductor wafer, is processed with a processing liquid. A single-substrate processing type apparatus that processes substrates one by one includes a spin chuck that rotates a substrate while holding the substrate substantially horizontally and a nozzle that supplies a processing liquid to a front surface of the substrate being rotated by the spin chuck.

In a typical substrate processing step, a chemical liquid is supplied to a substrate held by the spin chuck. Thereafter, a rinse liquid is supplied to the substrate, and, as a result, the chemical liquid on the substrate is replaced by the rinse liquid. Thereafter, a spin dry step is performed to exclude the rinse liquid on the substrate. In the spin dry step, the substrate is rotated at a high speed, and, as a result, the rinse liquid adhering to the substrate is shaken off and is removed (dried). A generally-used rinse liquid is deionized water.

A sublimation drying technique disclosed by Japanese Patent Application Publication No. 2010-199261 has been proposed in order to restrain or prevent the occurrence of a pattern collapse in the spin dry step. In Japanese Patent Application Publication No. 2010-199261, a frozen film is formed on a front surface of a substrate by supplying an ultra-low-temperature nitrogen gas (about −60° C.) to the front surface of the substrate. An aqueous component included in the frozen film of the front surface of the substrate is sublimated by continuing to supply the ultra-low-temperature nitrogen gas after the formation of the frozen film, and, as a result, the front surface of the substrate is dried without generating a liquid phase on the front surface of the substrate.

SUMMARY OF THE INVENTION

In the technique of Japanese Patent Application Publication No. 2010-199261, an ultra-low-temperature nitrogen gas (about −60° C.) is required to be continuously supplied to the substrate, and therefore equipment for supplying the nitrogen gas is needed, and there is a fear that running costs will become enormous.

The present inventors have considered that a solvent that has a sublimation capability and a low freezing point (as an example, a fluorine-based organic solvent that has a ring structure (freezing point of about 20.5° C.), tertiary butyl alcohol (freezing point of about 25° C.), or the like) is used as a sublimation agent, and have considered that a sublimation agent that is any one of these liquid sublimation agents is supplied to the front surface of the substrate, and have considered that a liquid having a temperature lower than the freezing point of the sublimation agent is supplied to a rear surface of the substrate as a temperature-controlling fluid for solidifying (freezing) a solvent of a sublimation agent. In detail, the present inventors supply cold water that has a liquid temperature of about 5° C. to about 15° C. to the rear surface of the substrate as a temperature-controlling liquid. Thereafter, a sublimation agent is cooled by supplying the cold water to the rear surface of the substrate, and as a result, the sublimation agent, such as a fluorine-based organic solvent having a ring structure or tertiary butyl alcohol, is solidified, and a sublimation-agent film is formed on the front surface of the substrate. Thereafter, the front surface of the substrate is dried by sublimating the sublimation-agent film.

However, in this technique, there is a fear that a water mist that has occurred in the rear surface of the substrate will flow around toward the front-surface side of the substrate, and water will mix with the sublimation-agent film that has been solidified. If water has mixed with the sublimation-agent film, there is a fear that the sublimation of the sublimation agent will be obstructed. Not only that, there is another fear that the pattern collapse will be promoted by the fact that water is liquefied in the surface of the substrate. That is, it is required to prevent contamination of water into the sublimation-agent film that has been solidified. Therefore, a solid sublimation-agent film has been desired to be excellently formed while preventing contamination of water into the solid sublimation-agent film.

Therefore, it is an object of the present invention to provide a substrate drying method and a substrate processing apparatus both of which are capable of excellently forming a solid sublimation-agent film while preventing contamination of water into the solid sublimation-agent film and hence capable of excellently realizing sublimation drying.

The present invention provides a substrate drying method including a sublimation-agent-liquid-film placing step of placing a liquid film of a liquid sublimation agent on the front surface of the substrate, a high vapor-pressure liquid supply step of supplying a high vapor-pressure liquid that has vapor pressure higher than the sublimation agent and that does not include water to a rear surface that is a surface on a side opposite to the front surface in the substrate, a vaporizing/cooling step of, after the liquid film of the sublimation agent is placed on the front surface of the substrate, stopping supplying the high vapor-pressure liquid, and, as a result, losing vaporization heat in response to vaporization of the high vapor-pressure liquid, and, as a result, cooling the sublimation agent, and, as a result, solidifying the liquid film of the sublimation agent, and, as a result, forming a sublimation-agent film on the front surface of the substrate, and a sublimating step of sublimating the sublimation-agent film.

According to this method, a liquid film of a sublimation agent (i.e., sublimation-agent liquid film) is placed on the front surface of the substrate. Furthermore, a high vapor-pressure liquid that has vapor pressure higher than the sublimation agent and that does not include water is supplied to the rear surface of the substrate. After the sublimation-agent liquid film is placed on the front surface of the substrate, the supply of the high vapor-pressure liquid is stopped. As a result, vaporization heat is lost from the substrate in response to vaporization of the high vapor-pressure liquid, and, as a result, a sublimation agent included in the sublimation-agent liquid film is cooled, and, as a result, the sublimation-agent liquid film is solidified. As a result, it is possible to excellently form a solid sublimation-agent film while preventing contamination of water into the solid sublimation-agent film.

Also, in the sublimating step, sublimating heat is lost in response to the sublimation of the sublimation-agent film, and the sublimation-agent film is kept at or below a freezing point (melting point). Therefore, it is possible to prevent the sublimation agent included in the sublimation-agent film from being melted. This makes it possible to excellently realize sublimation drying.

Also, the high vapor-pressure liquid does not include water, and therefore it is possible to supply the high vapor-pressure liquid to the whole area of the rear surface of the substrate without depending on whether the rear surface of the substrate presents hydrophobicity. This makes it possible to perform vaporizing and cooling in the whole area of the substrate, and hence makes it possible to evenly cool the sublimation agent in the plane of the substrate. This makes it possible to excellently solidify a sublimation agent included in the sublimation-agent liquid film.

In one preferred embodiment of the present invention, the high vapor-pressure liquid supplied to the rear surface of the substrate has a liquid temperature higher than the freezing point of the sublimation agent.

According to this method, the high vapor-pressure liquid supplied to the rear surface of the substrate has a liquid temperature higher than the freezing point of the sublimation agent. Therefore, the sublimation agent on the front surface of the substrate is not immediately cooled to or below the freezing point of the sublimation agent by the supply of the high vapor-pressure liquid to the substrate. Therefore, it is also possible to perform the disposition of a sublimation-agent liquid film on the front surface of the substrate and the supply of a high vapor-pressure liquid to the substrate in parallel with each other, and this also makes it possible to shorten the period of time of the entire processing.

Also, it is possible to use a high vapor-pressure liquid at a comparatively high liquid temperature. It is also possible to use the high vapor-pressure liquid at a room temperature depending on the kind of the high vapor-pressure liquid (for example, in a case in which a fluorine-based organic solvent whose freezing point is about 20.5° C. and that has a ring structure is employed as a sublimation agent). In this case, it is also possible to disuse a temperature control unit for high vapor-pressure liquids, and hence possible to reduce costs.

In one preferred embodiment of the present invention, the sublimation-agent-liquid-film placing step includes a sublimation-agent supply step of supplying a sublimation agent to the front surface of the substrate and a thinning step of, on the front surface of the substrate, thinning the sublimation agent supplied to the front surface of the substrate by rotating the substrate around a predetermined rotational axis without supplying a sublimation agent.

According to this method, it is possible to spread the sublimation agent by a centrifugal force generated by the rotation of the substrate on the front surface of the substrate. Consequently, it is possible to excellently form a sublimation agent that has an appropriate and small thickness on the front surface of the substrate, and it is possible to equalize the thickness of a sublimation-agent liquid film in the plane of the substrate.

In one preferred embodiment of the present invention, the high vapor-pressure liquid supply step is performed in parallel with the thinning step.

According to this method, the enlargement of the sublimation agent and the supply of a high vapor-pressure liquid to the substrate are performed in parallel with each other, and it is possible to shorten the period of time of the entire processing.

In one preferred embodiment of the present invention, the aforementioned method further includes a high-temperature liquid supply step of supplying a high-temperature liquid having a liquid temperature higher than a freezing point of a sublimation agent to the rear surface of the substrate in parallel with the sublimation-agent-liquid-film placing step.

According to this method, a high-temperature liquid having a liquid temperature higher than a freezing point of a sublimation agent is supplied to the rear surface of the substrate in parallel with the placement of the sublimation-agent liquid film on the front surface of the substrate. Therefore, it is possible to warm a sublimation agent supplied to the front surface of the substrate, and hence possible to prevent the sublimation agent from being immediately solidified. Therefore, it is possible to form an excellent sublimation-agent liquid film on the front surface of the substrate.

In one preferred embodiment of the present invention, the high-temperature liquid includes the high vapor-pressure liquid.

According to this method, it is possible to warm a sublimation agent supplied to the front surface of the substrate while more reliably preventing water from mixing with the sublimation-agent liquid film on the front surface of the substrate.

In one preferred embodiment of the present invention, the high-temperature liquid includes water.

According to this method, water is used as a high-temperature liquid, and therefore it is possible to make costs lower than in a case in which a high vapor-pressure liquid is used as a high-temperature liquid.

In one preferred embodiment of the present invention, the aforementioned method further includes a substrate rotating step of rotating the substrate around a predetermined rotational axis in parallel with at least either one of the sublimation-agent-liquid-film placing step and the vaporizing/cooling step and a high-speed rotation step of rotating the substrate around the predetermined rotational axis at a speed higher than in the substrate rotating step in parallel with the sublimating step.

According to this method, the substrate is rotated at a high speed in the sublimating step. The contact speed between the sublimation-agent film and its circumambient atmosphere is increased by the high-speed rotation of the substrate. This makes it possible to advance the sublimation of the sublimation-agent film, and hence makes it possible to sublimate the sublimation-agent film in a short time.

The present invention provides a substrate processing apparatus including a substrate holding unit that holds a substrate whose front surface has a pattern, a rotation unit that rotates a substrate held by the substrate holding unit around a predetermined rotational axis, a sublimation-agent supply unit that supplies a liquid sublimation agent to the front surface of the substrate, and a high vapor-pressure liquid supply unit that supplies a high vapor-pressure liquid that has vapor pressure higher than the sublimation agent and that does not include water to a rear surface that is a surface on a side opposite to the front surface in the substrate.

According to this arrangement, a sublimation agent is supplied to the front surface of the substrate. Consequently, a sublimation-agent liquid film is formed on the front surface of the substrate. Furthermore, a high vapor-pressure liquid that has vapor pressure higher than the sublimation agent and that does not include water is supplied to the rear surface of the substrate.

After the sublimation-agent liquid film is placed on the front surface of the substrate, the supply of the high vapor-pressure liquid is stopped. As a result, vaporization heat is lost from the substrate in response to vaporization of the high vapor-pressure liquid, and, as a result, a sublimation agent included in the sublimation-agent liquid film is cooled, and, as a result, the sublimation-agent liquid film is solidified. As a result, it is possible to excellently form a solid sublimation-agent film while preventing contamination of water into the solid sublimation-agent film. This makes it possible to excellently solidify the sublimation agent included in the sublimation-agent liquid film.

In one preferred embodiment of the present invention, the high vapor-pressure liquid supplied to the rear surface of the substrate has a liquid temperature higher than a freezing point of a sublimation agent.

According to this arrangement, the high vapor-pressure liquid supplied to the rear surface of the substrate has a liquid temperature higher than the freezing point of the sublimation agent. Therefore, the sublimation agent on the front surface of the substrate is not immediately cooled to or below the freezing point of the sublimation agent by the supply of the high vapor-pressure liquid to the substrate. Therefore, it is also possible to perform the disposition of a sublimation-agent liquid film on the front surface of the substrate and the supply of a high vapor-pressure liquid to the substrate in parallel with each other, and this also makes it possible to shorten the period of time of the entire processing.

Also, it is possible to use a high vapor-pressure liquid at a comparatively high liquid temperature. It is also possible to use the high vapor-pressure liquid at a room temperature depending on the kind of the high vapor-pressure liquid (for example, in a case in which a fluorine-based organic solvent whose freezing point is about 20.5° C. and that has a ring structure is employed as a sublimation agent). In this case, it is also possible to disuse a temperature control unit for high vapor-pressure liquids, and hence possible to reduce costs.

In one preferred embodiment of the present invention, the substrate processing apparatus further includes a controller that controls the rotation unit, the sublimation-agent supply unit, and the high vapor-pressure liquid supply unit. The controller may execute a sublimation-agent-liquid-film placing step of placing a liquid film of the sublimation agent on the front surface of the substrate by means of the rotation unit and the sublimation-agent supply unit, a high vapor-pressure liquid supply step of supplying a high vapor-pressure liquid to the rear surface of the substrate by means of the high vapor-pressure liquid supply unit, a vaporizing/cooling step of, after the liquid film of the sublimation agent is placed on the front surface of the substrate, stopping supplying the high vapor-pressure liquid, and, as a result, losing vaporization heat in response to vaporization of the high vapor-pressure liquid, and, as a result, cooling the sublimation agent, and, as a result, solidifying the liquid film of the sublimation agent, and, as a result, forming a sublimation-agent film on the front surface of the substrate, and a sublimating step of sublimating the sublimation-agent film by means of the rotation unit.

According to this arrangement, a liquid film of a sublimation agent is placed on the front surface of the substrate. Furthermore, a high vapor-pressure liquid that has vapor pressure higher than the sublimation agent and that does not include water is supplied to the rear surface of the substrate. After the sublimation-agent liquid film is placed on the front surface of the substrate, the supply of the high vapor-pressure liquid is stopped. As a result, vaporization heat is lost from the substrate in response to vaporization of the high vapor-pressure liquid, and, as a result, a sublimation agent included in the sublimation-agent liquid film is cooled, and, as a result, the sublimation-agent liquid film is solidified. As a result, it is possible to excellently form a solid sublimation-agent film while preventing contamination of water into the solid sublimation-agent film.

Also, in the sublimating step, sublimating heat is lost in response to the sublimation of the sublimation-agent film, and the sublimation-agent film is kept at or below a freezing point (melting point). Therefore, it is possible to prevent the sublimation agent included in the sublimation-agent film from being melted. This makes it possible to excellently realize sublimation drying.

Also, the high vapor-pressure liquid does not include water, and therefore it is possible to supply the high vapor-pressure liquid to the whole area of the rear surface of the substrate without depending on whether the rear surface of the substrate presents hydrophobicity. This makes it possible to perform vaporizing and cooling in the whole area of the substrate, and hence makes it possible to evenly cool the sublimation agent in the plane of the substrate. This makes it possible to excellently solidify a sublimation agent included in the sublimation-agent liquid film.

In one preferred embodiment of the present invention, the controller executes a sublimation-agent supply step of supplying a sublimation agent to the front surface of the substrate by means of the sublimation-agent supply unit in the sublimation-agent-liquid-film placing step and a thinning step of, on the front surface of the substrate, thinning the sublimation agent supplied to the front surface of the substrate by rotating the substrate around a predetermined rotational axis without supplying a sublimation agent by means of the rotation unit in the sublimation-agent-liquid-film placing step.

According to this arrangement, it is possible to spread the sublimation agent by a centrifugal force generated by the rotation of the substrate on the front surface of the substrate. Consequently, it is possible to excellently form a sublimation agent that has an appropriate and small thickness on the front surface of the substrate, and it is possible to equalize the thickness of a sublimation-agent liquid film in the plane of the substrate.

In one preferred embodiment of the present invention, the controller executes the high vapor-pressure liquid supply step in parallel with the thinning step.

According to this arrangement, the enlargement of the sublimation agent and the supply of a high vapor-pressure liquid to the substrate are performed in parallel with each other, and therefore it is possible to shorten the period of time of the entire processing.

In one preferred embodiment of the present invention, the substrate processing apparatus further includes a high-temperature liquid supply unit that supplies a high-temperature liquid having a liquid temperature higher than a freezing point of a sublimation agent to the rear surface of the substrate. The controller may further execute a high-temperature liquid supply step of supplying a high-temperature liquid having a liquid temperature higher than a freezing point of a sublimation agent to the rear surface of the substrate by means of the high-temperature liquid supply unit in parallel with the sublimation-agent-liquid-film placing step.

According to this arrangement, a high-temperature liquid having a liquid temperature higher than a freezing point of a sublimation agent is supplied to the rear surface of the substrate in parallel with the supply of a sublimation agent to the front surface of the substrate. Therefore, it is possible to warm a sublimation agent supplied to the front surface of the substrate, and hence possible to prevent the sublimation agent from being immediately solidified. Therefore, it is possible to form an excellent sublimation-agent liquid film on the front surface of the substrate.

In one preferred embodiment of the present invention, the high-temperature liquid includes the high vapor-pressure liquid.

According to this arrangement, it is possible to warm a sublimation agent supplied to the front surface of the substrate while more reliably preventing water from mixing with the sublimation-agent liquid film on the front surface of the substrate.

In one preferred embodiment of the present invention, the high-temperature liquid includes water.

According to this arrangement, water is used as a high-temperature liquid, and therefore it is possible to make costs lower than in a case in which a high vapor-pressure liquid is used as a high-temperature liquid.

In one preferred embodiment of the present invention, the controller further executes a substrate rotating step of rotating the substrate around a predetermined rotational axis in parallel with at least either one of the sublimation-agent-liquid-film placing step and the vaporizing/cooling step and a high-speed rotation step of rotating the substrate around the predetermined rotational axis at a speed higher than in the substrate rotating step in parallel with the sublimating step.

According to this arrangement, the substrate is rotated at a high speed in the sublimating step. The contact speed between the sublimation-agent film and its circumambient atmosphere is increased by the high-speed rotation of the substrate. This makes it possible to advance the sublimation of the sublimation-agent film, and hence makes it possible to sublimate the sublimation-agent film in a short time.

The aforementioned or other objects, features, and effects of the present invention will be clarified by the following description of preferred embodiments given below with reference to the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic view of a substrate processing apparatus, which is seen from above, according to a preferred embodiment of the present invention.

FIG. 2 is an illustrative cross-sectional view shown to describe an arrangement example of a processing unit included in the substrate processing apparatus.

FIG. 3 is a block diagram shown to describe an electrical configuration of a main part of the substrate processing apparatus.

FIG. 4 is an enlarged cross-sectional view of a front surface of a substrate that is to be processed by the substrate processing apparatus.

FIG. 5 is a flowchart shown to describe the contents of a first substrate processing example performed in the processing unit.

FIG. 6 is a flowchart shown to describe a sublimation drying step of FIG. 5.

FIG. 7A to FIG. 7D are schematic views, each showing a state around the substrate when the sublimation drying step is performed.

FIG. 8A and FIG. 8B are schematic views shown to describe a sublimation-agent supply step according to a second substrate processing example and a sublimation-agent supply step according to a third substrate processing example, respectively.

FIG. 9 shows a modification of the present invention.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

FIG. 1 is a schematic view of a substrate processing apparatus 1, which is seen from above, according to a preferred embodiment of the present invention. The substrate processing apparatus 1 is a single-substrate processing type apparatus that processes substrates W, such as silicon wafers, one by one. In the present preferred embodiment, the substrate W is a disk-shaped substrate. The substrate processing apparatus 1 includes a plurality of processing units 2 each of which processes a substrate W by use of a processing liquid and a rinse liquid, a load port LP at which a substrate container C that contains each of a plurality of substrates W that are processed by the processing units 2 is placed, an indexer robot IR and a substrate transfer robot CR each of which transfers a substrate W between the load port LP and the processing unit 2, and a controller 3 that controls the substrate processing apparatus 1. The indexer robot IR transfers the substrate W between the substrate container C and the substrate transfer robot CR. The substrate transfer robot CR transfers the substrate W between the indexer robot IR and the processing unit 2. The plurality of processing units 2 are identical, for example, in configuration with each other.

FIG. 2 is an illustrative cross-sectional view shown to describe an arrangement example of the processing unit 2.

The processing unit 2 includes a box-shaped chamber 4, a spin chuck (substrate holding unit) 5 that rotates a substrate W around a vertical rotational axis A1 passing through the center of the substrate W while holding the single substrate W in a horizontal attitude in the chamber 4, a sublimation-agent supply unit that supplies a liquid sublimation agent to an upper surface of the substrate W (a front surface Wa of the substrate W (see FIG. 4 and the like)) held by the spin chuck 5, a high vapor-pressure liquid supply unit that supplies IPA (isopropyl alcohol), which is an example of a high vapor-pressure liquid that has vapor pressure higher than water (i.e., vapor pressure higher than the sublimation agent) and that does not include water, to a lower surface of the substrate W (a rear surface Wb of the substrate W) held by the spin chuck 5, a shielding member 6 that faces the upper surface of the substrate W held by the spin chuck 5 and that blocks a space existing above the substrate W from its circumambient atmosphere, a lower-surface nozzle 7 that discharges a processing liquid toward a central part of the lower surface of the substrate W (the rear surface Wb of the substrate W (see FIG. 7A and the like)) held by the spin chuck 5, and a cylindrical processing cup 8 that surrounds the lateral side of the spin chuck 5.

The chamber 4 includes a box-shaped partition wall 11 that contains the spin chuck 5, etc.

A clamping-type chuck that clamps the substrate W in a horizontal direction and that horizontally holds the substrate W is employed as the spin chuck 5. In detail, the spin chuck 5 includes a spin motor (rotation unit) 12, a lower spin shaft 13 that is integrally united with a driving shaft of the spin motor 12, and a disk-shaped spin base 14 that is substantially horizontally attached to an upper end of the lower spin shaft 13.

The spin base 14 includes a horizontal and circular upper surface 14 a that has an outer diameter greater than that of the substrate W. A plurality of (three or more, e.g., six) clamping members 15 are disposed on the upper surface 14 a at its peripheral edge. The clamping members 15 are spaced out with suitable intervals there between, e.g., are spaced out evenly on a circumference corresponding to the outer peripheral shape of the substrate W at the peripheral edge of the upper surface of the spin base 14.

The shielding member 6 includes a shielding plate 17, an upper spin shaft 18 that is disposed at the shielding plate 17 so as to be rotatable together with the shielding plate 17, and an upper-surface nozzle 19 that passes through a central part of the shielding plate 17 in an up-down direction. The shielding plate 17 includes a disk portion 20 that is horizontally disposed and a cylindrical portion 21 that is disposed along an outer peripheral edge of the disk portion 20. The disk portion 20 is formed in a disk shape whose diameter is substantially equal to or greater than that of the substrate W. The disk portion 20 has its lower surface having a circular substrate-facing surface 20 a that faces the whole area of the upper surface of the substrate W. A cylindrical through hole 20 b that upwardly and downwardly passes through the disk portion 20 is formed in a central part of the substrate-facing surface 20 a. The through hole 20 b is defined by a cylindrical inner peripheral surface.

The cylindrical portion 21 may be formed in a truncated cone shape. The cylindrical portion 21 may extend downwardly so as to spread outwardly from the outer peripheral edge of the disk portion 20 as shown in FIG. 2. Also, the cylindrical portion 21 may become smaller in thickness in proportion to an approach to a lower end of the cylindrical portion 21 as shown in FIG. 2.

The upper spin shaft 18 is disposed rotatably around a rotational axis A2 (an axis that coincides with the rotational axis A1 of the substrate W) that passes through the center of the shielding plate 17 and that extends vertically. The upper spin shaft 18 is circularly cylindrical. An inner peripheral surface of the upper spin shaft 18 is formed at a cylindrical plane that centers on the rotational axis A2. An internal space of the upper spin shaft 18 communicates with the through hole 20 b of the shielding plate 17. The upper spin shaft 18 is relatively rotatably supported by a support arm 22 that horizontally extends above the shielding plate 17.

In the present preferred embodiment, the upper-surface nozzle 19 functions as a center shaft nozzle. The upper-surface nozzle 19 is disposed above the spin chuck 5. The upper-surface nozzle 19 is supported by the support arm 22. The upper-surface nozzle 19 is unrotatable with respect to the support arm 22. The upper-surface nozzle 19 moves up and down together with the shielding plate 17, the upper spin shaft 18, and the support arm 22. The upper-surface nozzle 19 has its lower end in which a discharge port 19 a that faces a central part of the upper surface of the substrate W held by the spin chuck 5 is formed.

A shielding-plate rotation unit 26 configured to include an electric motor and the like is joined to the shielding plate 17. The shielding-plate rotation unit 26 rotates the shielding plate 17 and the upper spin shaft 18 around the rotational axis A2 with respect to the support arm 22. A shielding-member lifting unit 27 configured to include an electric motor, a ball screw, etc., is joined to the support arm 22. The shielding-member lifting unit 27 raises and lowers the shielding member 6 (the shielding plate 17 and the upper spin shaft 18) and the upper-surface nozzle 19 together with the support arm 22 in a vertical direction.

The shielding-member lifting unit 27 raises and lowers the shielding plate 17 between a shielding position at which the substrate-facing surface 20 a approaches the upper surface of the substrate W held by the spin chuck 5 and at which the height of the lower end of the cylindrical portion 21 is placed below the height of the substrate W (shown by the alternate long and two short dashed line in FIG. 2. See also FIG. 7A and the like) and a retreat position that retreats greatly more upwardly than the shielding position (shown by the solid line in FIG. 2). The shielding-member lifting unit 27 is capable of holding the shielding plate 17 at the shielding position, at a nearby position (shown by the broken line in FIG. 2), and at the retreat position. The shielding position is a position at which the substrate-facing surface 20 a forms a shielding space 28 (see FIG. 7B and the like) between the upper surface of the substrate W and the substrate-facing surface 20 a. Although the shielding space 28 is not completely isolated from its circumambient space, a gas does not flow into the shielding space 28 from the circumambient space. In other words, the shielding space 28 is substantially shielded from its circumambient space. The nearby position is placed slightly above the retreat position. In a state in which the shielding plate 17 is placed at the nearby position, a space between the substrate-facing surface 20 a of the shielding plate 17 and the substrate W is not shielded from the circumambient space.

The sublimation-agent supply unit includes the upper-surface nozzle 19 and a sublimation agent unit 31 that supplies a liquid sublimation agent to the upper-surface nozzle 19. The sublimation agent unit 31 includes a sublimation agent pipe 32 connected to the upper-surface nozzle 19 and a sublimation agent valve 33 interposed in the sublimation agent pipe 32. The sublimation agent supplied to the sublimation agent pipe 32 is a solvent that has a sublimation capability and whose freezing point is low, and a solvent such as a fluorine-based organic solvent having a ring structure (whose freezing point is about 20.5° C.) or tertiary butyl alcohol (whose freezing point is about 25° C.) can be mentioned as an example. The sublimation agent supplied to the sublimation agent pipe 32 is a liquid sublimation agent whose temperature is slightly higher than the freezing point. In a case in which a fluorine-based organic solvent having a ring structure is employed as a sublimation agent, a sublimation agent having a room temperature (about 23° C. to about 25° C.) is given to the sublimation agent pipe 32. In a case in which tertiary butyl alcohol is employed as a sublimation agent, a sublimation agent that has undergone temperature control so as to have a temperature of about 30° C. is given to the sublimation agent pipe 32. A liquid sublimation agent is supplied to the upper-surface nozzle 19 by opening the sublimation agent valve 33, and, as a result, the liquid sublimation agent is discharged downwardly from the discharge port 19 a. The use of a fluorine-based organic solvent having a ring structure as a sublimation agent also makes it possible to disuse a temperature control unit for high vapor-pressure liquids, and it is possible to use the sublimation agent at a room temperature, and therefore it is possible to reduce costs.

An acid chemical-liquid supply unit 34, an alkaline chemical-liquid supply unit 35, a rinse-liquid supply unit 36, an organic-solvent supply unit 37, and a gas supply unit 38 are connected to the upper-surface nozzle 19.

The acid chemical-liquid supply unit 34 includes an acid chemical-liquid pipe 41 connected to the upper-surface nozzle 19 and an acid chemical-liquid valve 42 interposed in the acid chemical-liquid pipe 41. A chemical liquid including at least one of a group consisting of, for example, hydrofluoric acid (HF), hydrochloric acid, sulfuric acid, phosphoric acid, and nitric acid can be mentioned as an acid chemical liquid given to the acid chemical-liquid pipe 41. In the present preferred embodiment, hydrofluoric acid (HF) is employed as an acid chemical liquid. An acid chemical liquid is supplied to the upper-surface nozzle 19 by opening the acid chemical-liquid valve 42, and, as a result, the acid chemical liquid is discharged downwardly from the discharge port 19 a.

The alkaline chemical-liquid supply unit 35 includes an alkaline chemical-liquid pipe 43 connected to the upper-surface nozzle 19 and an alkaline chemical-liquid valve 44 interposed in the alkaline chemical-liquid pipe 43. A chemical liquid including at least one of a group consisting of, for example, ammonia and hydroxyl can be mentioned as an alkaline chemical liquid given to the alkaline chemical-liquid pipe 43. In the present preferred embodiment, SC1 (a liquid that includes NH₄OH and H₂O₂) is employed as an alkaline chemical liquid. An alkaline chemical liquid is supplied to the upper-surface nozzle 19 by opening the alkaline chemical-liquid valve 44, and, as a result, the alkaline chemical liquid is discharged downwardly from the discharge port 19 a.

The rinse-liquid supply unit 36 includes a rinse liquid pipe 45 connected to the upper-surface nozzle 19 and a rinse liquid valve 46 interposed in the rinse liquid pipe 45. A rinse liquid given to the rinse liquid pipe 45 is, for example, deionized water (DIW), and yet, without being limited to DIW, the rinse liquid may be any one of carbonated water, electrolyzed ion water, hydrogen water, ozone water, and hydrochloric acid water having a diluted concentration (for example, about 10 ppm to 100 ppm). A rinse liquid is supplied to the upper-surface nozzle 19 by opening the rinse liquid valve 46, and, as a result, the rinse liquid is discharged downwardly from the discharge port 19 a.

The organic-solvent supply unit 37 is a unit for supplying an organic solvent serving as a low-surface-tension liquid that is larger in specific gravity than air and that has surface tension lower than water. The organic-solvent supply unit 37 includes an organic solvent pipe 47 connected to the upper-surface nozzle 19 and an organic solvent valve 48 interposed in the organic solvent pipe 47. The organic solvent given to the organic solvent pipe 47 is, for example, IPA (isopropyl alcohol), and, for example, methanol, ethanol, acetone, EG (ethylene glycol), and HFE (hydrofluoroether) can be mentioned as the organic solvent, besides IPA. Also, a liquid mixed with other components may be used as the organic solvent without being limited to a monocomponent liquid. The organic solvent may be, for example, a mixed liquid of IPA and acetone, or may be, for example, a mixed liquid of IPA and methanol.

The gas supply unit 38 includes a gas supply pipe 49 connected to the upper-surface nozzle 19 and a gas valve 50 that opens and closes the gas supply pipe 49. The gas given to the gas supply pipe 49 is a dehumidified gas, particularly, a dehumidified inert gas. The inert gas includes, for example, a nitrogen gas and an argon gas. The gas is supplied to the upper-surface nozzle 19 by opening the gas valve 50, and, as a result, the gas is discharged downwardly from the discharge port 19 a.

The high vapor-pressure liquid supply unit includes the lower-surface nozzle 7 and a high vapor-pressure liquid unit 51 that supplies IPA (isopropyl alcohol), which is an example of a high vapor-pressure liquid, to the lower-surface nozzle 7.

The lower-surface nozzle 7 has a single discharge port 7 a facing the central part of the lower surface of the substrate W held by the spin chuck 5. The discharge port 7 a discharges a liquid vertically upwardly. The liquid discharged therefrom substantially perpendicularly strikes the central part of the lower surface of the substrate W held by the spin chuck 5. A lower-surface supply pipe 52 is connected to the lower-surface nozzle 7. The lower-surface supply pipe 52 is inserted into the inside of the lower spin shaft 13 that is a hollow shaft and that is disposed vertically.

The high vapor-pressure liquid unit 51 includes a high vapor-pressure liquid pipe 53 connected to the lower-surface supply pipe 52 and a high vapor-pressure liquid valve 54 interposed in the high vapor-pressure liquid pipe 53. A high vapor-pressure liquid given to the high vapor-pressure liquid pipe 53 is a liquid that has vapor pressure higher than water (vapor pressure higher than a sublimation agent) (i.e., that has a boiling point lower than water) and that does not include water. The high vapor-pressure liquid is, for example, a solvent, and, more specifically, is IPA (isopropyl alcohol). For example, methanol, ethanol, acetone, and HFE (hydrofluoroether) can be mentioned as the high vapor-pressure liquid (solvent), besides IPA. Also, a liquid mixed with other components may be used as the high vapor-pressure liquid without being limited to a monocomponent liquid. The high vapor-pressure liquid may be, for example, a mixed liquid of IPA and acetone, or may be, for example, a mixed liquid of IPA and methanol.

The temperature of the high vapor-pressure liquid supplied to the high vapor-pressure liquid pipe 53 is several degrees (° C.) higher than the freezing point of the sublimation agent (solvent) supplied to the sublimation agent pipe 32. In a case in which a fluorine-based organic solvent having a ring structure is employed as a sublimation agent supplied to the sublimation agent pipe 32, the high vapor-pressure liquid has a room temperature, and is given to the lower-surface supply pipe 52. In a case in which tertiary butyl alcohol is employed as a sublimation agent, the high vapor-pressure liquid has a temperature of about 30° C., and is given to the lower-surface supply pipe 52.

When the high vapor-pressure liquid valve 54 is opened, a high vapor-pressure liquid is supplied to the lower-surface nozzle 7 through the high vapor-pressure liquid pipe 53 and through the lower-surface supply pipe 52. The lower-surface nozzle 7 discharges the high vapor-pressure liquid supplied thereto substantially vertically upwardly from the discharge port 7 a, and the high vapor-pressure liquid discharged from the lower-surface nozzle 7 substantially perpendicularly strikes the central part of the lower surface of the substrate W held by the spin chuck 5.

The processing cup 8 is disposed at a more outward position than the substrate W held by the spin chuck 5 (in a direction away from the rotational axis A1). The processing cup 8 includes a plurality of cups 61 to 63 (first to third cups 61 to 63) surrounding the circumference of the spin base 14, a plurality of guards 64 to 66 (inner guard 64, intermediate guard 65, outer guard 66) each of which receives processing liquids (chemical liquid, rinse liquid, organic solvent, hydrophobizing agent, and the like) that have scattered around the substrate W, and a guard lifting unit 67 (see FIG. 5) that individually raises and lowers the plurality of guards 64 to 66. The processing cup 8 is disposed outside the outer periphery of the substrate W held by the spin chuck 5 (in the direction away from the rotational axis A1).

Each cup 61 to 63 is circularly cylindrical, and surrounds the periphery of the spin chuck 5. The second cup 62 that is the second from the inside is disposed outside the first cup 61, and the outermost third cup 63 is disposed outside the second cup 62. The third cup 63 is, for example, integrally united with the intermediate guard 65, and is raised and lowered together with the intermediate guard 65. Each cup 61 to 63 forms an annular groove that is upwardly opened.

A drainage pipe 76 is connected to the groove of the first cup 61. A processing liquid guided to the groove of the first cup 61 is sent to waste-liquid equipment placed outside the apparatus through the drainage pipe 76.

A collection pipe 77 is connected to the groove of the second cup 62. A processing liquid (chiefly, chemical liquid) guided to the groove of the second cup 62 is sent to the collection equipment placed outside the apparatus through the collection pipe 77, and is collected and processed in the collection equipment.

A collection pipe 78 is connected to the groove of the third cup 63. A processing liquid (for example, organic solvent) guided to the groove of the third cup 63 is sent to the collection equipment placed outside the apparatus through the collection pipe 78, and is collected and processed in the collection equipment.

Each guard 64 to 66 is circularly cylindrical, and surrounds the periphery of the spin chuck 5. Each guard 64 to 66 includes a cylindrical guide portion 68 that surrounds the periphery of the spin chuck 5 and a cylindrical inclined portion 69 that extends obliquely upwardly toward the center side from an upper end of the guide portion 68 (in a direction approaching the rotational axis A1 of the substrate W). An upper end part of each inclined portion 69 defines an inner peripheral part of each guard 64 to 66, and has a diameter greater than the substrate W and than the spin base 14. The three inclined portions 69 are piled together upwardly and downwardly, and the three guide portions 68 are disposed coaxially. The three guide portions 68 (guide portions 68 of the guards 64 to 66) are capable of coming into or out of the corresponding cups 61 to 63, respectively. In other words, the processing cup 8 is collapsible, and is folded and unfolded by allowing the guard lifting unit 67 to raise and lower at least one of the three guards 64 to 66. In the inclined portion 69, its sectional shape may be linear as shown in FIG. 2, or may extend, for example, smoothly while making a convex circular arc.

Each guard 64 to 66 is raised and lowered between an upper position (where the upper end part of each inclined portion 69 is placed above the upper surface of the substrate W) and a lower position (where the upper end part of each inclined portion 69 is placed below the upper surface of the substrate W) by driving the guard lifting unit 67.

In a state in which any one of the guards 64 to 66 faces a peripheral end surface of the substrate W, a processing liquid (acid chemical liquid, alkaline chemical liquid, rinse liquid, organic solvent, sublimation agent, high vapor-pressure liquid, etc.) is supplied to the substrate W, or the substrate W is dried. In order to realize a state in which, for example, the outermost outer guard 66 faces the peripheral end surface of the substrate W (state of FIG. 7D, which is hereinafter referred to as the “third guard facing state” when necessary), the inner guard 64 and the intermediate guard 65 are placed at the lower position, and the outer guard 66 is placed at the upper position. In the third guard facing state, all of the processing liquid discharged from the peripheral edge of the substrate W being in a rotational state is received by the outer guard 66.

In order to realize a state in which the intermediate guard 65, which is the second from the inside, faces the peripheral end surface of the substrate W (state of FIG. 7A, etc., which is hereinafter referred to as the “second guard facing state” when necessary), the inner guard 64 is placed at the lower position, and the intermediate guard 65 and the outer guard 66 are placed at the upper position. In the second guard facing state, all of the processing liquid discharged from the peripheral edge of the substrate W being in a rotational state is received by the intermediate guard 65.

In order to realize a state in which the innermost inner guard 64 faces the peripheral end surface of the substrate W (not shown, which is hereinafter referred to as the “first guard facing state” when necessary), all of the three guards 64 to 66 are placed at the upper position. In the first guard facing state, all of the processing liquid discharged from the peripheral edge of the substrate W being in a rotational state is received by the inner guard 64.

For example, in a state in which any one of the three guards 64 to 66 faces the peripheral end surface of the substrate W, a HF step S3 (see FIG. 5), a rinse step S4 (see FIG. 5), an SC1 step S5 (see FIG. 5), a rinse step S6 (see FIG. 5), a replacing step S7 (see FIG. 5), and a sublimation drying step S8 (see FIG. 5), which are described later, are performed. Therefore, a processing liquid that has scattered around the substrate W when a processing liquid is being supplied to the substrate W is guided to any one of the cups 61 to 63 by means of any one of the inner guard 64, the intermediate guard 65, and the outer guard 66.

FIG. 3 is a block diagram shown to describe an electrical configuration of a main part of the substrate processing apparatus 1.

The controller 3 is formed by use of, for example, a microcomputer. The controller 3 has an arithmetic unit, such as CPU, a storage unit, such as a read-only memory device and a hard disk drive, and an input-output unit. A program executed by the arithmetic unit is stored in the storage unit.

The spin motor 12, the shielding-member lifting unit 27, the shielding-plate rotation unit 26, the guard lifting unit 67, etc., which are to be controlled, are connected to the controller 3. The controller 3 controls the operations of the spin motor 12, the shielding-member lifting unit 27, the shielding-plate rotation unit 26, the guard lifting unit 67, etc., in accordance with a predetermined program.

Also, the controller 3 opens and closes the sublimation agent valve 33, the acid chemical-liquid valve 42, the alkaline chemical-liquid valve 44, the rinse liquid valve 46, the organic solvent valve 48, the gas valve 50, and the high vapor-pressure liquid valve 54 in accordance with a predetermined program.

A description will be hereinafter given of a case in which a substrate W having its front surface Wa that is a device-forming surface and on which a pattern 100 is formed is processed.

FIG. 4 is an enlarged cross-sectional view of a front surface Wa of a substrate W that is to be processed by the substrate processing apparatus 1. The substrate W to be processed is, for example, a silicon wafer. A pattern 100 is formed on the front surface Wa that is a pattern forming surface. The pattern 100 is, for example, a microscopic pattern. The pattern 100 may be a pattern in which structural elements 101 each of which has a convex shape (pillar shape) are disposed in a matrix manner as shown in FIG. 4. In this case, the pattern 100 is formed such that a line width W1 of the structural element 101 is, for example, about 3 nm to 45 nm and such that a gap W2 of the pattern 100 is, for example, about 10 nm to several μm, respectively. A film thickness T of the pattern 100 is, for example, about 0.2 μm to 1.0 μm. Also, the pattern 100 may be formed such that, for example, an aspect ratio (ratio of the film thickness T with respect to the line width W1) is, for example, about 5 to 500 (typically, it is about 5 to 50).

Also, the pattern 100 may be formed such that a linear pattern formed by a microscopic trench is repeatedly arranged. Also, the pattern 100 may be formed such that a plurality of microscopic holes (voids or pores) are made in a thin film.

The pattern 100 includes, for example, an insulating film. The pattern 100 may also include a conductor film. More specifically, the pattern 100 may be formed with a laminated film in which a plurality of films are stacked together, and may include an insulating film and a conductor film. The pattern 100 may be a pattern made of a single layer film. The insulating film may be a silicon oxide film (SiO₂ film) or may be a silicon nitride film (SiN film). Also, the conductor film may be an amorphous silicon film doped with impurities for low resistivity, or may be a metal film (for example, TiN film).

Also, the pattern 100 may be a hydrophilic film. A TEOS film (kind of silicon oxide film) can be mentioned as an example of the hydrophilic film.

FIG. 5 is a flowchart shown to describe the contents of a first substrate processing example performed in the processing unit 2. The first substrate processing example will be described with reference to FIG. 1 to FIG. 5.

An unprocessed substrate W (for example, a circular substrate having a diameter of 300 mm) is carried into the processing unit 2 from the substrate container C by means of the indexer robot IR and the substrate transfer robot CR, is then carried into the chamber 4, is then delivered to the spin chuck 5 in a state in which the front surface Wa (see FIG. 4 and the like) of the substrate W is directed upwardly, and is held by the spin chuck 5 (S1 of FIG. 5: Carry-in of Substrate W). In this state, the rear surface Wb of the substrate W (see FIG. 7A and the like) is directed downwardly. The substrate W is carried into the chamber 4 in a state in which the shielding plate 17 has been retreated to the retreat position and in a state in which the guards 64 to 66 have been placed at the lower position.

After the substrate transfer robot CR is retreated outwardly from the processing unit 2, the controller 3 increases the rotation speed of the spin base 14 to a predetermined liquid treatment speed (within the range of about 10 to 1200 rpm, e.g., about 300 rpm) while controlling the spin motor 12, and maintains the liquid treatment speed (S2 of FIG. 5: Start of rotation of Substrate W).

Furthermore, the controller 3 lowers the shielding plate 17 from the retreat position, and places it at the nearby position while controlling the shielding-member lifting unit 27.

Furthermore, the controller 3 allows the inner guard 64 to face the peripheral end surface of the substrate W (i.e., realizes a first guard facing state) by raising the inner guard 64, the intermediate guard 65, and the outer guard 66 to the upper position while controlling the guard lifting unit 67.

When the rotation of the substrate W reaches the liquid treatment speed, the controller 3 then performs the HF step S3 (see FIG. 5) in which HF, which is an example of an acid chemical liquid, is supplied to the front surface Wa of the substrate W. In detail, the controller 3 opens the acid chemical-liquid valve 42. As a result, HF is discharged from the discharge port 19 a of the upper-surface nozzle 19 toward the central part of the front surface Wa of the substrate W being in a rotational state. HF supplied to the front surface Wa of the substrate W moves to the peripheral edge of the substrate W while receiving a centrifugal force generated by the rotation of the substrate W. Consequently, the whole area of the front surface Wa of the substrate W is processed by use of HF.

HF that has moved to the peripheral edge of the substrate W is discharged from the peripheral edge of the substrate W in a lateral direction of the substrate W. HF discharged from the peripheral edge of the substrate W is received by an inner wall of the inner guard 64, is then allowed to flow down along the inner wall of the inner guard 64, and is sent to waste liquid treatment equipment placed outside the apparatus through the first cup 61 and through the drainage pipe 76.

When a predetermined period of time elapses from the start of discharge of HF, the controller 3 closes the acid chemical-liquid valve 42, and stops the discharge of HF from the upper-surface nozzle 19. Consequently, the HF step S3 is ended.

Thereafter, the controller 3 performs the rinse step S4 (see FIG. 5) in which a chemical liquid is excluded from on the substrate W by replacing HF present on the substrate W with a rinse liquid. In detail, the controller 3 opens the rinse liquid valve 46 while maintaining the first guard facing state of the processing cup 8. As a result, the rinse liquid is discharged from the discharge port 19 a of the upper-surface nozzle 19 toward the central part of the front surface Wa of the substrate W being in a rotational state. The rinse liquid supplied to the front surface Wa of the substrate W moves to the peripheral edge of the substrate W while receiving a centrifugal force generated by the rotation of the substrate W. Consequently, HF adhering to the surface of the substrate W is rinsed away by the rinse liquid.

The rinse liquid discharged from the peripheral edge of the substrate W is discharged from the peripheral edge of the substrate W in the lateral direction of the substrate W. The rinse liquid discharged from the peripheral edge of the substrate W is received by the inner wall of the inner guard 64, is then allowed to flow down along the inner wall of the inner guard 64, and is sent to the waste liquid treatment equipment placed outside the apparatus through the first cup 61 and through the drainage pipe 76. When a predetermined period of time elapses from the open of the rinse liquid valve 46, the controller 3 closes the rinse liquid valve 46. Consequently, the rinse step S4 is ended.

Thereafter, the controller 3 performs the SC1 step S5 (see FIG. 5) in which SC1 that is an example of an alkaline chemical liquid is supplied to the front surface Wa of the substrate W. In detail, the controller 3 opens the alkaline chemical-liquid valve 44. As a result, SC1 is discharged from the discharge port 19 a of the upper-surface nozzle 19 toward the central part of the front surface Wa of the substrate W being in a rotational state. SC1 supplied to the front surface Wa of the substrate W moves to the peripheral edge of the substrate W while receiving a centrifugal force generated by the rotation of the substrate W. Consequently, the whole area of the front surface Wa of the substrate W is processed by use of SC1.

SC1 that has moved to the peripheral edge of the substrate W is discharged from the peripheral edge of the substrate W in the lateral direction of the substrate W. SC1 discharged from the peripheral edge of the substrate W is received by the inner wall of the inner guard 64, is then allowed to flow down along the inner wall of the inner guard 64, and is sent to the waste liquid treatment equipment placed outside the apparatus through the first cup 61 and through the drainage pipe 76.

When a predetermined period of time elapses from the start of discharge of SC1, the controller 3 closes the alkaline chemical-liquid valve 44, and stops the discharge of SC1 from the upper-surface nozzle 19. Consequently, the SC1 step S5 is ended.

Thereafter, the controller 3 performs the rinse step S6 (see FIG. 5) in which a chemical liquid is excluded from on the substrate W by replacing SC1 present on the substrate W with a rinse liquid. In detail, the controller 3 opens the rinse liquid valve 46 while maintaining the first guard facing state of the processing cup 8. As a result, the rinse liquid is discharged from the discharge port 19 a of the upper-surface nozzle 19 toward the central part of the front surface Wa of the substrate W being in a rotational state. The rinse liquid supplied to the front surface Wa of the substrate W moves to the peripheral edge of the substrate W while receiving a centrifugal force generated by the rotation of the substrate W. Consequently, SC1 adhering to the surface of the substrate W is rinsed away by the rinse liquid.

The rinse liquid discharged from the peripheral edge of the substrate W is discharged from the peripheral edge of the substrate W in the lateral direction of the substrate W. The rinse liquid discharged from the peripheral edge of the substrate W is received by the inner wall of the inner guard 64, is then allowed to flow down along the inner wall of the inner guard 64, and is sent to the waste liquid treatment equipment placed outside the apparatus through the first cup 61 and through the drainage pipe 76. When a predetermined period of time elapses from the open of the rinse liquid valve 46, the controller 3 closes the rinse liquid valve 46. Consequently, the rinse step S6 is ended.

Thereafter, the controller 3 performs the replacing step S7 (see FIG. 5). The replacing step S7 is a step in which a rinse liquid on the substrate W is replaced by an organic solvent (in this example, IPA) that is lower in surface tension than the rinse liquid (water). The controller 3 allows the outer guard 66 to face the peripheral end surface of the substrate W (i.e., realizes a third guard facing state) by lowering the inner guard 64 and the intermediate guard 65 to the lower position while controlling the guard lifting unit 67.

Furthermore, the controller 3 opens the organic solvent valve 48. As a result, IPA is discharged from the discharge port 19 a of the upper-surface nozzle 19 toward the central part of the front surface Wa of the substrate W being in a rotational state. IPA supplied to the front surface Wa of the substrate W receives a centrifugal force generated by the rotation of the substrate W, and spreads over the whole area of the front surface Wa of the substrate W. Consequently, in the whole area of the front surface Wa of the substrate W, the rinse liquid adhering to the front surface Wa is replaced by an organic solvent. The organic solvent that moves on the front surface Wa of the substrate W is discharged from the peripheral edge of the substrate W in the lateral direction of the substrate W. The organic solvent discharged from the peripheral edge of the substrate W is received by the inner wall of the outer guard 66, is then allowed to flow down along the inner wall of the outer guard 66, and is sent to the collection equipment through the third cup 63 and the collection pipe 78.

When a predetermined period of time elapses from the open of the organic solvent valve 48, the controller 3 closes the organic solvent valve 48. Consequently, the replacing step S7 is ended.

Furthermore, after the end of the replacing step S7, the controller 3 performs the sublimation drying step S8 (see FIG. 5). In the sublimation drying step S8, a liquid sublimation agent is supplied to the front surface Wa of the substrate W, and a liquid film that is thick enough to soak the pattern 100 is formed on the front surface Wa of the substrate W, and then a sublimation-agent film is formed by solidifying the liquid film. Thereafter, a sublimation agent included in the sublimation-agent film is sublimated by rotating the substrate W at a high speed. In this case, a liquid phase does not exist between the patterns 100 of the front surface Wa of the substrate W when the substrate W is rotated at a high speed, and therefore it is possible to dry the substrate W while lessening the problem of the pattern collapse. The sublimation drying step S8 will be described in detail as follows.

When a predetermined period of time elapses from the start of the high-speed rotation in the sublimation drying step S8, the controller 3 stops the rotation of the spin chuck 5 while controlling the spin motor 12 (S9 of FIG. 5: Stop of Rotation of Substrate W). Furthermore, the controller 3 lowers the outer guard 66 while controlling the guard lifting unit 67, and allows all guards to retreat downwardly from the peripheral end surface of the substrate W.

Thereafter, the substrate transfer robot CR enters the processing unit 2, and carries an already-processed substrate W out of the processing unit 2 (S10 of FIG. 5: Carry-out of Substrate W). The substrate W carried out therefrom is delivered to the indexer robot IR from the substrate transfer robot CR, and is stored in the substrate container C by means of the indexer robot IR.

FIG. 6 is a flowchart shown to describe the sublimation drying step S8 of FIG. 5. FIG. 7A to FIG. 7D are schematic views, each showing a state around the substrate W when the sublimation drying step S8 is performed.

The sublimation drying step S8 includes a sublimation-agent-liquid-film placing step T10 in which a liquid film (i.e., a sublimation-agent liquid film) 81 of a liquid sublimation agent is placed on the front surface Wa of the substrate W, a high vapor-pressure liquid supply step in which a high vapor-pressure liquid that has vapor pressure higher than water (vapor pressure higher than a sublimation agent) and that does not include water is supplied to the rear surface Wb of the substrate W, and a vaporizing/cooling step T3 in which the supply of a high vapor-pressure liquid to the rear surface Wb is stopped after the sublimation-agent liquid film 81 is placed on the front surface Wa of the substrate W, and, as a result, vaporization heat is lost in response to the vaporization of the high vapor-pressure liquid, and, as a result, a sublimation agent included in the sublimation-agent liquid film 81 is cooled. The sublimation agent included in the sublimation-agent liquid film 81 is solidified by performing the vaporizing/cooling step T3, and a solid sublimation-agent film 82 is formed on the front surface Wa of the substrate W. The sublimation drying step S8 also includes a sublimating step T4 that sublimates the sublimation-agent film 82.

The sublimation-agent-liquid-film placing step T10 includes a sublimation-agent supply step T1 in which a sublimation agent is supplied to the front surface Wa of the substrate W and a thinning step T2 in which the sublimation agent supplied thereto is thinly spread (is thinned) on the front surface Wa of the substrate W by rotating the substrate W around the rotational axis A1 without supplying a sublimation agent.

In the sublimation drying step S8, there is a fear that the sublimation of the sublimation agent will be obstructed if water is mixed with the sublimation-agent film 82 that has been solidified. Not only that, there is another fear that the pattern collapse will be promoted by the fact that water is liquefied in the surface of the substrate W. Therefore, the sublimation drying step S8 is required to be performed in a state in which moisture has been excluded from the front surface Wa of the substrate W as much as possible so that water does not mix with the sublimation-agent liquid film 81 or does not mix with the sublimation-agent film 82 that has been solidified (i.e., while maintaining the front surface Wa of the substrate W at a low humidity). Therefore, the sublimation drying step S8 is performed in the shielding space 28 (see FIG. 7A and the like).

When the sublimation drying step S8 (sublimation-agent supply step T1) is started, the controller 3 lowers the shielding plate 17 from the nearby position to the shielding position while controlling the shielding-member lifting unit 27. Consequently, the shielding space 28 is formed between the substrate-facing surface 20 a and the front surface Wa of the substrate W. Furthermore, the controller 3 lowers the inner guard 64 to the lower position while controlling the guard lifting unit 67, and, as a result, allows the intermediate guard 65 to face the peripheral end surface of the substrate W (i.e., realizes a second guard facing state).

Thereafter, the controller 3 performs the sublimation-agent supply step T1. In detail, the controller 3 opens the sublimation agent valve 33 while keeping the rotation of the substrate W at the liquid treatment speed. As a result, a liquid sublimation agent is discharged from the discharge port 19 a of the upper-surface nozzle 19 toward the central part of the front surface Wa of the substrate W being in a rotational state. The sublimation agent supplied to the front surface Wa of the substrate W receives a centrifugal force generated by the rotation of the substrate W, and moves to the peripheral edge of the substrate W. Consequently, a sublimation-agent liquid film 80 with which the whole area of the front surface Wa of the substrate W is covered is formed as shown in FIG. 7A.

In the sublimation-agent supply step T1, the controller 3 supplies a high vapor-pressure liquid (high-temperature liquid) from the discharge port 7 a of the lower-surface nozzle 7 toward the central part of the rear surface Wb of the substrate W in parallel with the supply of a sublimation agent to the front surface Wa of the substrate W. This high vapor-pressure liquid has a liquid temperature that is several degrees (° C.) higher than the freezing point of the sublimation agent supplied to the front surface Wa of the substrate W. A high vapor-pressure liquid having such a liquid temperature is supplied to the rear surface Wb of the substrate W, and therefore it is possible to prevent immediate solidification. Therefore, it is possible to form an excellent sublimation-agent liquid film on the front surface of the substrate.

Also, a high vapor-pressure liquid (i.e., IPA) is used as a liquid (high-temperature liquid) for the prevention of solidification as mentioned above, and therefore it is possible to warm a sublimation agent supplied to the front surface Wa of the substrate W while more reliably preventing water from mixing with the sublimation-agent liquid film 80 on the front surface Wa of the substrate W.

When such a period of time as to enable the sublimation-agent liquid film 80 to cover the whole area of the front surface Wa of the substrate W elapses, the controller 3 closes the sublimation agent valve 33. Consequently, the sublimation-agent supply step T1 is ended.

Thereafter, the controller 3 performs the thinning step T2. The substrate W is rotated at a liquid treatment speed (about 300 rpm) while closing the sublimation agent valve 33 (i.e., in a state of stopping the supply of the sublimation agent from the upper-surface nozzle 19). In the thinning step T2, it is possible to spread the sublimation agent by a centrifugal force generated by the rotation of the substrate W on the front surface Wa of the substrate W. The thickness of the sublimation-agent liquid film 81 that has been thinned is, for example, about 10 μm. Consequently, it is possible to excellently form the sublimation-agent liquid film 81 that has an appropriate and small thickness on the front surface Wa of the substrate W, and it is possible to equalize the thickness of the sublimation-agent liquid film 81 in the plane of the substrate W.

Also, in the thinning step T2, the controller 3 supplies a high vapor-pressure liquid from the discharge port 7 a of the lower-surface nozzle 7 toward the central part of the rear surface Wb of the substrate W. This high vapor-pressure liquid has a liquid temperature (T_(IPA)) that is several degrees (° C.) higher than the freezing point (FP) of the sublimation agent supplied to the front surface Wa of the substrate W (T_(IPA)>FP). Therefore, the sublimation-agent liquid film 81 on the front surface Wa of the substrate W is not immediately cooled to or below the freezing point of the sublimation agent by the supply of the high vapor-pressure liquid to the substrate W. The supply of a high vapor-pressure liquid to the rear surface Wb of the substrate W in the thinning step T2 continuously follows the supply of a high vapor-pressure liquid to the rear surface Wb of the substrate W in the sublimation-agent supply step T1.

The high vapor-pressure liquid is a solvent that does not include water, and therefore it is possible to allow the high vapor-pressure liquid to spread over the whole area of the rear surface Wb of the substrate W without depending on whether the rear surface Wb of the substrate W presents hydrophobicity. Consequently, a liquid film 84 of a high vapor-pressure liquid with which the whole area of the rear surface Wb of the substrate W is covered is formed.

When a predetermined period of time elapses from the closing of the sublimation agent valve 33, the controller closes the high vapor-pressure liquid valve 54. Consequently, the supply of a high vapor-pressure liquid to the rear surface Wb of the substrate W is stopped. Consequently, the thinning step T2 is ended.

Thereafter, the controller 3 performs the vaporizing/cooling step T3. The substrate W continues to rotate at the liquid treatment speed during the vaporizing/cooling step T3.

After the supply of the high vapor-pressure liquid to the rear surface Wb of the substrate W is stopped, the vaporization of the high vapor-pressure liquid having a high vapor pressure is advanced in the rear surface Wb of the substrate W. The heat of vaporization is lost from the rear surface Wb in response to the vaporization of the high vapor-pressure liquid in the rear surface Wb of the substrate W. Consequently, the substrate W is cooled, and the sublimation agent included in the sublimation-agent liquid film 81 formed on the front surface Wa of the substrate W is also cooled. In response to the cooling, the sublimation agent included in the sublimation-agent liquid film 81 is reduced in temperature to or below the freezing point (FP) of the sublimation agent (more specifically, lower in temperature than the freezing point (FP)). Consequently, the sublimation agent included in the sublimation-agent liquid film 81 is solidified. A solid sublimation-agent film 82 is formed on the front surface Wa of the substrate W by the fact that all of the sublimation agent included in the sublimation-agent liquid film 81 is solidified. The temperature Ts of the sublimation-agent film 82 is lower than the freezing point (FP>Ts).

In the present preferred embodiment, the liquid film 84 of a high vapor-pressure liquid with which the whole area of the rear surface Wb of the substrate W is covered is formed in the thinning step T2. Therefore, the high vapor-pressure liquid is vaporized in the whole area of the substrate W in the vaporizing/cooling step T3, and vaporizing/cooling is performed in the whole area of the substrate W, and therefore the sublimation agent is evenly cooled in the plane of the substrate W.

When a predetermined period of time elapses from the closing of the high vapor-pressure liquid valve 54, the vaporizing/cooling step T3 is ended.

Thereafter, the controller 3 performs the sublimating step T4. The controller 3 lowers the intermediate guard 65 to the lower position while controlling the guard lifting unit 67, and, as a result, allows the outer guard 66 to face the peripheral end surface of the substrate W (i.e., realizes a third guard facing state). Furthermore, the controller 3 accelerates the rotation of the substrate W to a high speed (e.g., about 1500 rpm) (rotational speed higher than in the sublimation-agent-liquid-film placing step T10 and in the vaporizing/cooling step T3). Furthermore, the controller 3 allows the shielding plate 17 to rotate at a speed equal to that of the rotation of the substrate W and in the same direction as the rotation of the substrate W while controlling the shielding-plate rotation unit 26. The contact speed between the sublimation-agent film 82 and its circumambient atmosphere is increased in response to the high-speed rotation of the substrate W. This makes it possible to advance the sublimation of the sublimation-agent film 82, and hence makes it possible to sublimate the sublimation-agent film in a short time.

Furthermore, the controller 3 opens the gas valve 50 in the sublimating step T4. As a result, a dehumidified gas is discharged from the discharge port 19 a of the upper-surface nozzle 19 toward the central part of the front surface Wa of the substrate W being in a rotational state. This makes it possible to perform the sublimating step T4 while keeping the shielding space 28 in a low humidity state.

In the sublimating step T4, sublimating heat is lost in response to the sublimation of the sublimation-agent film 82, and the sublimation-agent film 82 is kept at or below the freezing point (melting point). Therefore, it is possible to prevent the sublimation agent included in the sublimation-agent film 82 from being melted. This makes it possible to excellently realize sublimation drying.

As described above, according to the present preferred embodiment, the sublimation-agent liquid film 81 is placed on the front surface Wa of the substrate W. Also, a high vapor-pressure liquid is supplied to the rear surface Wb of the substrate W. After the sublimation-agent liquid film 81 is placed on the front surface Wa of the substrate W, the supply of the high vapor-pressure liquid is stopped. Consequently, the sublimation agent included in the sublimation-agent liquid film is cooled by the fact that the heat of vaporization is lost from the substrate W in response to the vaporization of the high vapor-pressure liquid, and the sublimation-agent liquid film 81 is solidified. This makes it possible to excellently form the solid sublimation-agent film 82 while preventing contamination of water into the solid sublimation-agent film 82.

Also, in the sublimating step T4, sublimating heat is lost in response to the sublimation of the sublimation-agent film 82, and the sublimation-agent film 82 is kept at or below the freezing point (melting point). Therefore, it is possible to prevent the sublimation agent included in the sublimation-agent film 82 from being melted. This makes it possible to excellently realize sublimation drying.

Also, the high vapor-pressure liquid does not include water, and therefore it is possible to supply the high vapor-pressure liquid to the whole area of the rear surface Wb of the substrate W without depending on whether the rear surface Wb of the substrate W presents hydrophobicity. This makes it possible to perform vaporizing and cooling in the whole area of the substrate W, and hence makes it possible to evenly cool the sublimation agent in the plane of the substrate W. This makes it possible to excellently solidify the sublimation agent included in the sublimation-agent liquid film 81.

Also, a high vapor-pressure liquid supplied to the rear surface Wb of the substrate W has a liquid temperature higher than the freezing point of a sublimation agent. Therefore, the sublimation agent on the front surface Wa of the substrate W is not immediately cooled to or below the freezing point of the sublimation agent by the supply of the high vapor-pressure liquid to the substrate W. Therefore, it is also possible to perform the disposition of a sublimation-agent liquid film on the front surface Wa of the substrate W and the supply of a high vapor-pressure liquid to the substrate W in parallel with each other, and this also makes it possible to shorten the period of time of the entire processing.

FIG. 8A is a schematic view shown to describe a sublimation-agent supply step according to a second substrate processing example.

A point of difference in which the second substrate processing example differs from the first substrate processing example is that water, not a high vapor-pressure liquid (IPA), is supplied to the rear surface Wb of the substrate W in parallel with the sublimation-agent supply step T1.

As shown by the broken line in FIG. 2, the processing unit 2 may also include a water supply unit 151 that supplies water to the rear surface Wb of the substrate W (i.e., to a lower surface of the substrate W) held by the spin chuck 5. The water supply unit 151 includes the lower-surface nozzle 7, the lower-surface supply pipe 52, a water pipe 152 connected to the lower-surface supply pipe 52, and a water valve 153 interposed in the water pipe 152. A water supply source is supplied to the water pipe 152. DIW (deionized water) can be mentioned as this water, and yet carbonated water, electrolyzed ion water, hydrogen water, ozone water, hydrochloric acid water having a diluted concentration (e.g., about 10 to 100 ppm), restoration water (hydrogen water), ammonia water, degassed water, etc., may be used.

Water is supplied to the rear surface Wb of the substrate W by opening the water valve 153. The supply of water is continuously performed until the end of the sublimation-agent supply step T1, and is stopped at a timing at which the thinning step is started (i.e., at a timing at which the supply of a sublimation agent to the front surface of the substrate W is stopped).

According to the second substrate processing example, water is used as a liquid (high-temperature liquid) for the prevention of solidification, and therefore it is possible to make costs lower than in a case in which a high vapor-pressure liquid is used as a high-temperature liquid.

Although one preferred embodiment of the present invention has been described as above, the present invention can also be embodied in other modes.

For example, the supply of a liquid (high-temperature liquid) for the prevention of solidification to the rear surface Wb, which is performed in parallel with the sublimation-agent supply step T1, may be started before starting the sublimation-agent supply step T1. Also, it is permissible not to supply a liquid (high-temperature liquid) for the prevention of solidification to the rear surface Wb of the substrate W in parallel with the sublimation-agent supply step T1 as in a third substrate processing example of FIG. 8B.

Also, it is also possible to exclude the thinning step T2. In this case, a high vapor-pressure liquid may be supplied to the rear surface Wb of the substrate Win parallel with the sublimation-agent supply step T1, and the supply of the high vapor-pressure liquid to the rear surface Wb of the substrate W may be stopped immediately after the end of the sublimation-agent supply step T1 (i.e., the vaporizing/cooling step T3 may be started immediately).

Also, although a sublimation agent is supplied by the upper-surface nozzle 19 that passes through the shielding plate 17 upwardly and downwardly as described in the above preferred embodiment, the sublimation agent can be supplied by another nozzle. In this case, it is also possible to supply a sublimation agent by use of a gas discharge nozzle 201 capable of radially discharging a gas in the lateral direction as shown in FIG. 9.

The gas discharge nozzle 201 has a cylindrical nozzle body 204 having a flange portion 203 at its lower end. A gas discharge port 205 and a gas discharge port 206 are outwardly bored in an outer peripheral surface, which is a side surface of the flange portion 203, in annular forms, respectively. A center gas-discharge port 207 is disposed at a lower surface of the nozzle body 204. Therefore, a three-layer radial airflow made by combining together a radial airflow formed by an inert gas discharged from the center gas-discharge port 207 and a two-layer radial airflow discharged from the gas discharge ports 205 and 206 is formed above the substrate W.

A liquid nozzle 208 is inserted in the nozzle body 204 upwardly and downwardly. A discharge port 209 formed at a lower end of the liquid nozzle 208 faces a space below the nozzle body 204. A liquid sublimation agent is supplied to the liquid nozzle 208, and, accordingly, the sublimation agent is discharged downwardly from the discharge port 209. Likewise, in this case, it is possible to supply the sublimation agent to the front surface Wa of the substrate W while removing moisture from the front surface Wa of the substrate W.

Also, although the substrate processing apparatus 1 is an apparatus that processes a substrate W of a semiconductor wafer as described in the aforementioned preferred embodiment, the substrate processing apparatus may be an apparatus that processes substrates, such as substrates for liquid crystal displays, substrates for FPDs (Flat Panel Displays) such as organic EL (electroluminescence) displays, substrates for optical disks, substrates for magnetic disks, substrates for magneto-optical disks, substrates for photomasks, ceramic substrates, and substrates for solar cells.

Although the preferred embodiments of the present invention have been described in detail, these preferred embodiments are merely concrete examples used to clarify the technical contents of the present invention, and the present invention should not be understood by being limited to these concrete examples, and the scope of the present invention is limited solely by the appended claims.

This application corresponds to Japanese Patent Application No. 2017-167866 filed in the Japan Patent Office on Aug. 31, 2017, and the entire disclosure of the application is incorporated herein by reference. 

What is claimed is:
 1. A substrate drying method for drying a front surface of a substrate having a pattern, the substrate drying method comprising: a sublimation-agent-liquid-film placing step of placing a liquid film of a liquid sublimation agent on the front surface of the substrate; a high vapor-pressure liquid supply step of supplying a high vapor-pressure liquid that has vapor pressure higher than the sublimation agent and that does not include water to a rear surface that is a surface on a side opposite to the front surface in the substrate; a vaporizing/cooling step of, after the liquid film of the sublimation agent is placed on the front surface of the substrate, stopping supplying the high vapor-pressure liquid, and, as a result, losing vaporization heat in response to vaporization of the high vapor-pressure liquid, and, as a result, cooling the sublimation agent, and, as a result, solidifying the liquid film of the sublimation agent, and, as a result, forming a sublimation-agent film on the front surface of the substrate; and a sublimating step of sublimating the sublimation-agent film.
 2. The substrate drying method according to claim 1, wherein the high vapor-pressure liquid supplied to the rear surface of the substrate has a liquid temperature higher than a freezing point of a sublimation agent.
 3. The substrate drying method according to claim 1, wherein the sublimation-agent-liquid-film placing step comprises: a sublimation-agent supply step of supplying a sublimation agent to the front surface of the substrate; and a thinning step of, on the front surface of the substrate, thinning the sublimation agent supplied to the front surface of the substrate by rotating the substrate around a predetermined rotational axis without supplying a sublimation agent.
 4. The substrate drying method according to claim 3, wherein the high vapor-pressure liquid supply step is performed in parallel with the thinning step.
 5. The substrate drying method according to claim 1, further comprising a high-temperature liquid supply step of supplying a high-temperature liquid having a liquid temperature higher than a freezing point of a sublimation agent to the rear surface of the substrate in parallel with the sublimation-agent-liquid-film placing step.
 6. The substrate drying method according to claim 5, wherein the high-temperature liquid includes the high vapor-pressure liquid.
 7. The substrate drying method according to claim 5, wherein the high-temperature liquid includes water.
 8. The substrate drying method according to claim 1, further comprising: a substrate rotating step of rotating the substrate around a predetermined rotational axis in parallel with at least either one of the sublimation-agent-liquid-film placing step and the vaporizing/cooling step; and a high-speed rotation step of rotating the substrate around the predetermined rotational axis at a speed higher than in the substrate rotating step in parallel with the sublimating step.
 9. A substrate processing apparatus comprising: a substrate holding unit that holds a substrate whose front surface has a pattern; a rotation unit that rotates a substrate held by the substrate holding unit around a predetermined rotational axis; a sublimation-agent supply unit that supplies a liquid sublimation agent to the front surface of the substrate; and a high vapor-pressure liquid supply unit that supplies a high vapor-pressure liquid that has vapor pressure higher than the sublimation agent and that does not include water to a rear surface that is a surface on a side opposite to the front surface in the substrate.
 10. The substrate processing apparatus according to claim 9, wherein the high vapor-pressure liquid supplied to the rear surface of the substrate has a liquid temperature higher than a freezing point of a sublimation agent.
 11. The substrate processing apparatus according to claim 9 further comprising a controller that controls the rotation unit, the sublimation-agent supply unit, and the high vapor-pressure liquid supply unit, the controller executing: a sublimation-agent-liquid-film placing step of placing a liquid film of the sublimation agent on the front surface of the substrate by means of the rotation unit and the sublimation-agent supply unit; a high vapor-pressure liquid supply step of supplying a high vapor-pressure liquid to the rear surface of the substrate by means of the high vapor-pressure liquid supply unit; a vaporizing/cooling step of, after the liquid film of the sublimation agent is placed on the front surface of the substrate, stopping supplying the high vapor-pressure liquid, and, as a result, losing vaporization heat in response to vaporization of the high vapor-pressure liquid, and, as a result, cooling the sublimation agent, and, as a result, solidifying the liquid film of the sublimation agent, and, as a result, forming a sublimation-agent film on the front surface of the substrate; and a sublimating step of sublimating the sublimation-agent film by means of the rotation unit.
 12. The substrate processing apparatus according to claim 11, wherein the controller executes: a sublimation-agent supply step of supplying a sublimation agent to the front surface of the substrate by means of the sublimation-agent supply unit in the sublimation-agent-liquid-film placing step; and a thinning step of, on the front surface of the substrate, thinning the sublimation agent supplied to the front surface of the substrate by rotating the substrate around a predetermined rotational axis without supplying a sublimation agent by means of the rotation unit in the sublimation-agent-liquid-film placing step.
 13. The substrate processing apparatus according to claim 12, wherein the controller executes the high vapor-pressure liquid supply step in parallel with the thinning step.
 14. The substrate processing apparatus according to claim 11, further comprising a high-temperature liquid supply unit that supplies a high-temperature liquid having a liquid temperature higher than a freezing point of a sublimation agent to the rear surface of the substrate, wherein the controller further executes a high-temperature liquid supply step of supplying a high-temperature liquid having a liquid temperature higher than a freezing point of a sublimation agent to the rear surface of the substrate by means of the high-temperature liquid supply unit in parallel with the sublimation-agent-liquid-film placing step.
 15. The substrate processing apparatus according to claim 14, wherein the high-temperature liquid includes the high vapor-pressure liquid.
 16. The substrate processing apparatus according to claim 14, wherein the high-temperature liquid includes water.
 17. The substrate processing apparatus according to claim 11, wherein the controller further executes: a substrate rotating step of rotating the substrate around a predetermined rotational axis in parallel with at least either one of the sublimation-agent-liquid-film placing step and the vaporizing/cooling step; and a high-speed rotation step of rotating the substrate around the predetermined rotational axis at a speed higher than in the substrate rotating step in parallel with the sublimating step. 